Note: Descriptions are shown in the official language in which they were submitted.
METHODS FOR MANAGING HERBICIDE VAPORIZATION USING A WATER
CONDITIONING ADJUVANT COMPRISING AN AMINE SURFACTANT AND A
MINERAL ACID
[0001]
FIELD OF THE INVENTION
[0002] The present application relates to compositions for spray
application to
agricultural land and methods for preparing such compositions. Specifically,
the present
application relates to water conditioning adjuvants which either do not
increase or effectively
reduce the vaporization of certain herbicides. The present application also
relates to methods
for managing the vaporization of herbicides such that vaporization of
herbicides is not
increased or is reduced. The present application further relates to
combination water
conditioning adjuvant and drift reduction compositions which can be added to
agricultural
chemicals, such as herbicides to be sprayed on crops, for the purpose of
improving efficacy
and reducing drift of the sprayed chemicals away from the target areas.
BACKGROUND
[0003] There exists keen interest in the agricultural industry to
provide crops such as
corn, soybean and cotton resistance to multiple herbicides, due to the
development of
resistance to individual herbicides in many pest species. In particular,
agricultural companies
are developing crops with tolerance to both glyphosate and either 2,4-D ((2,4-
dichlorophenoxy)acetic acid) or dicamba (3,6-dichloro-o-anisic acid).
[0004] Hard water, when used as a carrier for spray solutions, can
adversely affect the
effectiveness of certain salt-formulated herbicides such as glyphosate,
sethoxydim,
imazethapyr, glufosinate, 2,4-D amine salt and dicamba. Natural waters usually
contain ions
of calcium (Ca+2), magnesium (Mg+2), and iron (Fe+3). Hard water ions can bind
with salts of
certain herbicides and with some surfactants to form insoluble salts and
reduce the
effectiveness of herbicides and surfactants.
[0005] Adding agents such as ammonium sulfate (AMS), has been shown to
increase
herbicide efficacy on a broad spectrum of weed species under hard water
conditions.
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Presumably, AMS acts as a hard water cation scavenger. In the agricultural
industry there is a
move away from the use of AMS. Yet, certain AMS replacement adjuvants increase
the
vaporization of herbicides, such as dicamba and 2,4-D, which is detrimental to
the efficacy of
these herbicides.
[0006] There exists a pressing need in the agricultural industry for AMS
replacement
adjuvants and methods for producing agricultural spray compositions containing
herbicides
which do not increase or effectively reduce the vaporization of the
herbicides.
[0007] In addition to the problem presented by increased vaporization of
herbicides is
the problem of herbicide spray drift which is the movement of herbicides from
the target area
to areas where herbicide application was not intended. Herbicide spray drift
may injure
susceptible crops and could cause prohibited residues in the harvested crops.
Drift can cause
non-uniform application in a field with possible crop damage and/or poor weed
control. Drift
can also cause surface water contamination and health risks for animals and
people. Spray
drift can be reduced by increasing droplet size of the spray, as wind moves
larger droplets
less than smaller droplets.
[0008] U.S. Patent No. 6,797,673 to Worthley et al. entitled "Lecithin-
Containing
Drift Control Composition for Use in Spraying Agricultural Acreage" discloses
the use of
lecithin as drift reduction agent in a composition comprising a methyl ester
and a non-ionic
surfactant. U.S. Patent No. 4,681,617 to Ghyczy et al. entitled "Phospholipid
Compositions
and their Use in Plant Protection Spray Mixtures" discloses the use of
phospholipids as drift
reduction agents.
[0009] Further to the need for AMS replacement adjuvants and methods for
producing agricultural spray compositions containing herbicides which do not
increase or
effectively reduce the vaporization of the herbicides is the needs for such
AMS replacement
adjuvants and methods for producing agricultural spray compositions containing
herbicides
which also reduce spray drift.
SUMMARY
[0010] The present disclosure provides water conditioning adjuvants and
drift
reduction compositions combined with water conditioning adjuvants for
agricultural use
which do not increase or effectively reduce the vaporization of the
herbicides. Compositions
are disclosed comprising a water conditioning adjuvant comprising a
concentrated mineral
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acid and an amine surfactant and also disclosed are compositions further
comprising a drift
reduction agent.
[0011] Also disclosed are processes for preparing a water conditioning
adjuvant as
well as a combination water conditioning adjuvant and drift reduction
composition for
agricultural use comprising adding a concentrated mineral acid to an amine
surfactant to
obtain a water conditioning adjuvant and optionally adding the water
conditioning adjuvant to
a drift reduction agent.
[0012] Further disclosed are methods for reducing drift during release of
agricultural
chemicals comprising a combination water conditioning adjuvant and drift
reduction
composition comprising forming an aqueous composition suitable for treating
agricultural
acreage by mixing a combination water conditioning adjuvant and drift
reduction
composition for agricultural use, carrier water and a bioactive material and
spraying the
aqueous composition on agricultural acreage.
[0013] Further disclosed are methods for conditioning hard water, including
reducing
the negative impact of hard water cations on herbicide efficacy, while not
increasing
herbicide vaporization or while reducing herbicide vaporization. In
particular, methods and
compositions are disclosed, wherein polyamine is combined with strong mineral
acid and
further combined with a bioactive material, wherein the volatility or
vaporization of the
bioactive material is not increased or is reduced. In one embodiment, a
polyamine is
combined with sulfuric acid to produce an adjuvant which when combined with an
herbicide,
for example dicamba or 2,4-D, results in the volatility or vaporization of the
herbicide being
not increased or reduced.
[0014] In some embodiments, the method for conditioning water in an
agricultural
spray mixture comprises at least one herbicide wherein vaporization of the
herbicide is either
not increased or is reduced comprising: (a) providing an aqueous solution
comprising at least
one herbicide selected from the group consisting of dicamba and 2,4-D; (b)
providing an
adjuvant consisting essentially of an effective amount of a mineral acid
selected from the
group consisting of sulfuric acid, perchloric acid, hydroiodic acid,
hydrobromic acid,
hydrochloric acid and nitric acid and a polyamine surfactant combined in an
agricultural
spray solution wherein said adjuvant does not contain ammonium sulfate (AMS);
(c) mixing
a ratio equivalent to 1 quart to 2 gallons of the adjuvant of (b) to 100
gallons of (a); and (d)
maintaining the pH of the mixture of (a) and (b) at a pH above 2.3. In some
embodiments of
the method for conditioning water in an agricultural spray mixture, the acid
has the ability to
completely or nearly completely dissociate in water and react with cations. In
some
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embodiments of the method for conditioning water in an agricultural spray
mixture, the
polyamine surfactant is a fatty amine alkoxylate. In some embodiments of the
method for
conditioning water in an agricultural spray mixture, the polyamine surfactant
is a fatty amine
ethoxylate. In some embodiments of the method for conditioning water in an
agricultural
spray mixture, the polyamine surfactant is tallow amine ethoxylate. In some
embodiments of
the method for conditioning water in an agricultural spray mixture, the
combination of the
aqueous solution of (a) and the adjuvant of (b) has a pH of between 1.2 and
3.1 below the
aqueous solution of (a) without the adjuvant of (b). In some embodiments of
the method for
conditioning water in an agricultural spray mixture, the aqueous solution of
(a) has a pH
within the range of 7.2-7.5. In some embodiments of the method for
conditioning water in an
agricultural spray mixture, the adjuvant of (b) has a pH within the range of
1.9-2.1. In some
embodiments of the method for conditioning water in an agricultural spray
mixture, the
aqueous solution of (a) has a pH within the range of 4.3-6.3. In some
embodiments of the
method for conditioning water in an agricultural spray mixture, the mineral
acid is
concentrated sulfuric acid. In some embodiments of the method for conditioning
water in an
agricultural spray mixture, the aqueous solution of (a) has a pH in a range
from 7.2-7.5; the
adjuvant of (b) has a pH in a range of 1.9-2.1; and the combination of the
aqueous solution of
(a) and the adjuvant of (b) has a pH in a range from 4.3-6.3. In some
embodiments of the
method for conditioning water in an agricultural spray mixture, the aqueous
solution of (a)
has a pH in a range from 7.2-7.5; the adjuvant of (b) has a pH in a range of
1.9-2.1; and the
combination of the aqueous solution of (a) and the adjuvant of (b) has a pH in
a range from
4.4-4.5. In some embodiments of the method for conditioning water in an
agricultural spray
mixture, the aqueous solution of (a) has a pH in a range from 7.2-7.5; the
adjuvant of (b) has
a pH in a range of 1.9-2.1; and the combination of the aqueous solution of (a)
and the
adjuvant of (b) has a pH in a range from 4.3-4.5. In some embodiments of the
method for
conditioning water in an agricultural spray mixture, the aqueous solution of
(a) has a pH in a
range from 7.2-7.5; the adjuvant of (b) has a pH in a range of 1.9-2.1; and
the combination of
the aqueous solution of (a) and the adjuvant of (b) has a pH in a range from
5.2-5.7. In some
embodiments of the method for conditioning water in an agricultural spray
mixture, the
aqueous solution of (a) has a pH in a range from 7.2-7.5; the adjuvant of (b)
has a pH in a
range of 1.9-2.1; and the combination of the aqueous solution of (a) and the
adjuvant of (b)
has a pH in a range from 6-6.3.
[0015] In a further embodiment, the method for conditioning water in an
agricultural
spray mixture comprising at least one herbicide wherein vaporization of the
herbicide is
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either not increased or is reduced comprises: (a) providing an aqueous
solution comprising at
least one herbicide selected from the group consisting of dicamba and 2,4-D;
(b) providing an
adjuvant consisting essentially of an effective amount of a mineral acid
selected from the
group consisting of sulfuric acid, perchloric acid, hydroiodic acid,
hydrobromic acid,
hydrochloric acid and nitric acid, a polyamine surfactant and an antifoam
agent combined in
an agricultural spray solution wherein said adjuvant does not contain ammonium
sulfate
(AMS); (c) mixing a ratio equivalent to 1 quart to 2 gallons of the adjuvant
of (b) to 100
gallons of (a); and (d) maintaining the pH of the mixture of (a) and (b) at a
pH above 2.3. In
some embodiments of the method for conditioning water in an agricultural spray
mixture,
step (c) comprises mixing a ratio equivalent to 1 quart to 1 gallon of the
adjuvant of (b) to
100 gallons of (a).
[00161 In an additional embodiment, the method for conditioning water in
and
reducing drift of an agricultural spray mixture comprising at least one
herbicide wherein
vaporization of the herbicide is either not increased or is reduced comprises:
(a) providing an
aqueous solution comprising at least one herbicide selected from the group
consisting of
dicamba and 2,4-D; (b) providing a water conditioning adjuvant comprising an
amine
surfactant and a concentrated mineral acid selected from the group consisting
of sulfuric acid,
perchloric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, and
nitric acid; and a
drift reduction agent selected from the group consisting of at least one
phospholipid,
vegetable colloids, non-derivatized guar gum, non-cationic derivatized guar
gum, cationic
guar gum, polyethylene oxides, poly (vinyl pyrrolidones), polyacrylamides, a
non-ionic
emulsifier, a cationic emulsifier which is not an amine surfactant, and an
anionic emulsifier;
and (c) mixing the aqueous solution of (a) with the adjuvant of (b). In some
embodiments of
the method for conditioning water in and reducing drift of an agricultural
spray mixture, the
drift reduction agent is at least one phospholipid. In some embodiments of the
method for
conditioning water in and reducing drift of an agricultural spray mixture, the
drift reduction
agent is at least one phospholipid and the at least one phospholipid is
selected from the group
consisting of lecithin, phosphatidic acid, phosphotidyl ethanolamine,
phosphatidylcholine,
phosphatidylserine, phosphatidylinositol, phosphatidylinositol phosphate,
phosphatidylinositol biphosphate, phosphatidylinositol triphosphate, and
mixtures thereof. In
some embodiments of the method for conditioning water in and reducing drift of
an
agricultural spray mixture, the drift reduction agent is at least one
phospholipid and the at
least one phospholipid is lecithin. In some embodiments of the method for
conditioning water
in and reducing drift of an agricultural spray mixture, the concentrated
mineral acid is
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sulfuric acid. In some embodiments of the method for conditioning water in and
reducing
drift of an agricultural spray mixture, the concentrated mineral acid is
sulfuric acid and the
concentrated sulfuric acid is selected from the group consisting of 93% to 98%
concentrated
sulfuric acid. In some embodiments of the method for conditioning water in and
reducing
drift of an agricultural spray mixture, the amine surfactant is selected from
the group
consisting of octyl amine, lauryl amine, stearyl amine, ()ley' amine, tallow
amine, cetylamine,
N-tetradecyl amine, cocoamine, hydrogenated tallow amine, di(hydrogenated)
tallow amine,
dicocoalkyl amine, N-tridecyltridecanamine, N-methylstearylamine, distearyl
amine, ether
amine and dialkyl (C8-C20) amine. In some embodiments of the method for
conditioning
water in and reducing drift of an agricultural spray mixture, the amine
surfactant is tallow
amine. In some embodiments of the method for conditioning water in and
reducing drift of an
agricultural spray mixture, the amine surfactant is tallow amine and the
concentration of
tallow amine is equal to or greater than the concentration of sulfuric acid in
the adjuvant. In
some embodiments of the method for conditioning water in and reducing drift of
an
agricultural spray mixture, the adjuvant further comprises an oil selected
from the group
consisting of free fatty acid, mineral oil, vegetable oil, methylated seed
oil, ethylated seed oil,
butylated seed oil, and mixtures thereof. In some embodiments of the method
for
conditioning water in and reducing drift of an agricultural spray mixture, the
adjuvant further
comprises an oil selected from soybean oil, sunflower oil, cotton seed oil,
crop oil
concentrate and methylated soybean oil. In some embodiments of the method for
conditioning water in and reducing drift of an agricultural spray mixture, the
adjuvant further
comprises methylated seed oil. In some embodiments of the method for
conditioning water
in and reducing drift of an agricultural spray mixture, the adjuvant further
comprises a glycol
selected from the group consisting of diethylene glycol, triethylene glycol,
tetraethylene
glycol and pentaethylene glycol. In some embodiments of the method for
conditioning water
in and reducing drift of an agricultural spray mixture, the adjuvant further
comprises a non-
ionic surfactant selected from the group consisting of an alkyl
polyoxyethylene ether,
polyoxypropylene glycol, an alkyl phenol ethoxylate, an alcohol ethoxylate, a
sugar ether, a
sucrose ester, a sorbitan ester ethoxylate, a crop oil concentrate, morpholine
amide and a
block copolymer. In some embodiments of the method for conditioning water in
and
reducing drift of an agricultural spray mixture, the adjuvant does not contain
and is not
contacted with ammonium sulfate (AMS). In some embodiments of the method for
conditioning water in and reducing drift of an agricultural spray mixture, the
adjuvant
comprises an emulsifier. In some embodiments of the method for conditioning
water in and
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reducing drift of an agricultural spray mixture, the adjuvant comprises an
additive selected
from a buffering agent, a defoaming agent, a wetting agent, a sticking agent
and a tank
cleaner. In some embodiments of the method for conditioning water in and
reducing drift of
an agricultural spray mixture, the water content of the adjuvant is below 5 %
(v/v), before
dilution of the composition in carrier water. In some embodiments of the
method for
conditioning water in and reducing drift of an agricultural spray mixture, the
water content of
the adjuvant is below 1 % (v/v), before dilution of the composition in carrier
water. In some
embodiments of the method for conditioning water in and reducing drift of an
agricultural
spray mixture, the adjuvant comprises 1-25% by weight or volume concentrated
mineral acid,
10-50% by weight or volume amine surfactant, 10-60% by weight or volume
phospholipid,
10-50% by weight or volume oil and 5-50% by weight or volume glycol. In some
embodiments of the method for conditioning water in and reducing drift of an
agricultural
spray mixture, the adjuvant comprises 1-25% by weight or volume concentrated
sulfuric acid,
10-50% by weight or volume tallow amine, 10-60% by weight or volume lecithin,
10-50% by
weight or volume methylated seed oil and 5-50% by weight or volume diethylene
glycol. In
some embodiments of the method for conditioning water in and reducing drift of
an
agricultural spray mixture, the non-ionic emulsifier is selected from the
group consisting of
alcohols, alcohol ethoxylates, polyoxyethylene-polyoxypropylene-alkyl ethers,
amine
alkoxylates, fatty alcohol polyglycol ethers, fatty amine polyglycol ethers,
fatty acid
ethoxylates, fatty acid polyglycol esters, glyceride monoalkoxylates,
alkanolamides, fatty
acid alkanolamides, ethoxylated alkanolamides, ethoxylated esters, fatty acid
alkylolamido
ethoxylates, ethylene oxide-propylene oxide block copolymers, alkylphenol
ethoxylates,
alkyl glucosides, partial esters of aliphatic carboxylic acids with
polyfunctional alcohols,
polyethoxylated polystyrene phenyl ethers, amides of aliphatic carboxylic
acids with
alkanolamines, ethoxylated amides of aliphatic carboxylic acids with
alkanolamines,
morpholine amide and polyalkoxylated organopoly-siloxanes. In some embodiments
of the
method for conditioning water in and reducing drift of an agricultural spray
mixture, the
cationic emulsifier is selected from the group consisting of primary,
secondary and tertiary
amines and salts thereof, alkyltrimethylammonium salts,
dialkyldimethylammonium salts,
trialkylmethylammonium salts, tetraalkylammonium salts, alkoxylated
alkylammonium salts,
ester quats, diamidoamine quats, alkyloxyalkyl quats, quaternary
alkylphosphonium salts,
tertiary alkylsulfonium salts, alkylimidazolium salts, alkyloxazolinium salts,
alkylpyridium
salts and N,N-dialkylmorpholinium salts; the cationic emulsifier may comprise
chloride,
bromide, methyl sulfate, sulfate or the like as counterion. In some
embodiments of the
7
method for conditioning water in and reducing drift of an agricultural spray
mixture, the
anionic emulsifier is selected from the group consisting of alkyl sulfates,
arylsulfonates, fatty
alcohol sulfates, alkylsulfonates, paraffinsulfonates, alkyl ether sulfates,
alkyl polyglycol
ether sulfates, fatty alcohol ether sulfates, alkylbenzenesulfonates,
alkylnaphthylsulfonates,
alkylphenyl ether sulfates, alkyl phosphates, phosphoric acid mono-, di-, and
tri-esters, alkyl
ether phosphates, ethoxylated fatty alcohol phosphoric esters, alkylphenyl
ether phosphates,
phosphonic esters, sulfosuccinic diesters, sulfosuccinic monoesters,
ethoxylated sulfosuccinic
monoesters, sulfosuccinamides, a olefinsulfonates, alkyl carboxylates, alkyl
ether
carboxylates, alkyl polyglycol carboxylates, fatty acid isethionate, fatty
acid methyltauride,
fatty acid sarcoside, arylsulfonates, naphthalenesulfonates, alkyl glyceryl
ether sulfonates,
sulfated oils, polyacrylates and/or cc-sulfa fatty acid esters. In some
embodiments of the
method for conditioning water in and reducing drift of an agricultural spray
mixture, the
adjuvant comprises a free fatty acid selected from the group consisting of
free C12-C18
saturated and unsaturated fatty acid. In some embodiments of the method for
conditioning
water in and reducing drift of an agricultural spray mixture, the adjuvant
comprises a sugar
ether selected from the group consisting of glucoside alkyl ether, xylose
alkyl ether,
arabinose alkyl ether, mannose alkyl ether, ribose alkyl ether, rhamnose alkyl
ether,
galactose alkyl ether, sucrose alkyl ether, maltose alkyl ether, lactose alkyl
ether, fructose
alkyl ether, and raffinose alkyl ether.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 illustrates the relative control of 4 indicator plant
species using
ROUNDUP in combination with one of FULL LOAD (a water conditioning adjuvant),
AIR
LINK (commercial standard drift reduction agent) and AQ 162 (combination water
conditioning adjuvant and drift reduction composition).
[0018] Figure 2 illustrates spray droplet size comparing two
combination water
conditioning adjuvant and drift reduction compositions, AQ 163 and AQ 162 at a
concentration of 0.25% v/v, to commercial drift reduction standards AIR LINK
and
INTERLOCK at the same concentration.
[0019] Figure 3 illustrates the results of greenhouse box tests for
dicamba vapor
injury. CLARITY (dicamba DGA salt 0.25 lbae/acre), 20 mls of a spray solution
equal to 20
gallons/acre spray volume was placed in a Petrie dish next to soybean plants
in a box for 48
hours. The results show the state of the plants 8 days after application, as
well as 18 days
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after application. Addition of the Load Out (AQ119) adjuvant as described in
Example 15,
Table 12 showed a decrease in the volatility injury rating compared to the
absence of
adjuvant (labeled CLARITY) and compared to competitor adjuvant products HEL-
FIRE and
BRIMESTONE (both contain urea in combination with sulfuric acid) which
substantially
increased dicamba vaporization and consequently caused more injury. Addition
of Full Load
Complete (AQ1000) as described in Example 12 (disclosed elsewhere herein as AQ
284)
showed a decrease in the volatility injury rating compared to the absence of
adjuvant (labeled
CLARITY) and compared to competitor adjuvant products HEL-FIRE and BRIMESTONE.
Addition of Full Load (AQ127) as described Table 14 showed a substantial
decrease in the
volatility injury rating compared to the absence of adjuvant (labeled CLARITY)
and
compared to competitor adjuvant products HEL-FIRE and BRIMESTONE.
[0020] Figure 4 illustrates the results of greenhouse box tests for dicamba
vapor
injury run with the same materials and methods as the results shown in Figure
3. CLARITY
(dicamba DGA salt 0.25 lbae/acre, spray volume equal to 20 gallons/acre) was
placed in a
Petrie dish next to soybean plants in a box for 48 hours. The results show the
state of the
plants 8 days after application. Addition of the Load Out adjuvant as
described in Example
15, Table 12 did not increase the volatility injury rating compared to the
absence of adjuvant
(labeled CLARITY). In contrast, competitor adjuvant products HEL-FIRE and
BRIMESTONE (both contain urea in combination with sulfuric acid) substantially
increased
dicamba vaporization and consequently caused more injury.
[0021] Figure 5 illustrates the results of greenhouse box tests for 2,4-D
vapor injury.
2,4-D DMA (2,4-D amine salt 0.5 lbae/acre). 20 mls of a spray solution equal
to 20
gallons/acre spray volume was placed in a Petrie dish next to tomato plants in
a box for 48
hours. The results show the state of the plants 18 days after application.
Addition of the Full
Load Complete (AQ1000) as described in Example 12 (disclosed elsewhere herein
as AQ
284) showed a decrease in the volatility injury rating compared to the absence
of adjuvant
(labeled 2,4-D DMA) and compared to competitor adjuvant products HEL-FIRE and
BRIMESTONE (both contain urea in combination with sulfuric acid) which
substantially
increased 2,4-D vaporization and consequently caused more injury. Addition of
Full Load
(AQ127) as described Table 14 showed a substantial decrease in the volatility
injury rating
compared to the absence of adjuvant (labeled 2,4-D DMA) and compared to
competitor
adjuvant products HEL-FIRE and BRIMESTONE.
[0022] Figure 6 illustrates the results of greenhouse box tests for 2,4-D
vapor injury
to tomatoes. 20 mls of 2,4-D DMA (2,4-D amine salt use rate 0.25 lbs/acre) was
placed in a
9
Petrie dish next to tomato plants in a box for 48 hours. The results show the
state of the plants
28 days after application. Addition of the Load Out adjuvant as described in
Example 15,
Table 12 reduced the volatility injury rating compared to AMS. The photographs
of the
plants show tomato plants exposed to vapor from 2,4-D DMA salt and AMS (17
lbs/100
gallons); 2,4-D DMA salt and Load Out (0.5 % v/v); and untreated control
plants.
DETAILED DESCRIPTION
[0023] Reference will now be made in detail to representative
embodiments of the
invention. While the invention will be described in conjunction with the
enumerated
embodiments, it will be understood that the invention is not intended to be
limited to those
embodiments. On the contrary, the invention is intended to cover all
alternatives,
modifications, and equivalents that may be included within the scope of the
present invention
as defined by the claims.
[0024] One skilled in the art will recognize many methods and
compositions similar
or equivalent to those described herein, which could be used in and are within
the scope of
the practice of the present invention. The present invention is in no way
limited to the
methods and compositions described.
[0025] Unless defined otherwise, technical and scientific terms used
herein have the
same meaning as commonly understood by one of ordinary skill in the art(s) to
which this
invention belongs. Although any methods, processes, and compositions similar
or equivalent
to those described herein can be used in the practice or testing of the
invention, the preferred
methods, processes and compositions are now described.
[0026] All publications, published patent documents, and patent
applications cited in
this disclosure are indicative of the level of skill in the art(s) to which
the disclosure pertains.
[0027] As used in this disclosure, including the appended claims, the
singular forms
"a," "an," and "the" include plural references, unless the content clearly
dictates otherwise,
and are used interchangeably with "at least one" and "one or more."
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[0028] As used herein, the term "about" represents an insignificant
modification or
variation of the numerical value such that the basic function of the item to
which the
numerical value relates is unchanged.
[0029] As used herein, the term "use in agriculture" or "agricultural use"
means use
of methods, processes or compositions in the cultivation of plants.
[0030] As used herein, the term "adjuvant" means a composition which
increases the
efficacy of a bioactive material, including but not limited to increasing the
efficacy of a
herbicide.
[0031] As used herein, the term "bioactive material" means agricultural
chemicals,
including but not limited to pesticides, herbicides, fungicides, insecticides,
acaricides,
nematocides, foliar nutrients, defoliants, plant growth regulators, and
molluscicides.
[0032] As used herein, the term "carrier water" means water used to dilute
agricultural chemicals, including but not limited to spray application of such
chemicals.
[0033] As used herein, the term "drift" or "spray drift" means the movement
of a
bioactive material from the target area to areas where application of the
bioactive material
was not intended.
[0034] As used herein, the term "drift reduction agent" or "drift reduction
composition" means a composition which can reduce drift or spray drift, by
means including
but not limited to increasing the droplet size of a sprayed liquid. The drift
reduction agent or
drift reduction composition includes but is not limited to phospholipids (e.g.
lecithin),
vegetable colloids, non-derivatized guar gum, non-cationic derivatized guar
gum, cationic
guar gum, polyethylene oxides, poly (vinyl pyrrolidones), polyacrylamides, a
non-ionic
emulsifier, a cationic emulsifier and an anionic emulsifier.
[0035] As used herein, the term -lecithin" means a composition comprising
one or
more types of phospholipids, including but not limited to phosphatidylcholine,
phosphatidylethanolamine, phosphatidylserine, and phosphatidylinositol.
Lecithin may
further comprise compositions, including but not limited to triglycerides,
fatty acids,
glycolipids and carbohydrates. Lecithin may be derived from sources including
but not
limited to soy, safflower, sunflower, and rapeseed.
[0036] As used herein, the term "mineral acid" means an acid, optionally a
concentrated mineral acid, which does not comprise any carbon atoms, including
but not
limited to sulfuric acid, perchloric acid, hydroiodic acid, hydrobromic acid,
hydrochloric
acid, and nitric acid. As used herein, the term "mineral acid" does not
include phosphoric
acid. As used herein, the term -concentrated mineral acid" includes but is not
limited to
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sulfuric acid more than 90% concentrated, perchloric acid that is more than
50%
concentrated, hydroiodic acid which is more than 40% concentrated, hydrobromic
acid which
is more than 50% concentrated, hydrochloric acid which is more than 25%
concentrated, and
nitric acid which is more than 60% concentrated.
[0037] As used herein, the term "amine surfactant" means a surfactant
comprising an
amine group, including but not limited to octyl amine, lauryl amine, stearyl
amine, oleyl
amine, tallow amine, cetylamine, N-tetradecyl amine. cocoamine, hydrogenated
tallow
amine, di(hydrogenated) tallow amine, dicocoalkyl amine, N-
tridecyltridecanamine, N-
methylstearylamine, distearyl amine, ether amine and dialkyl (C8-C/0) amine.
Amine
surfactants include cationic surfactants such as alkyl dimethylamines, alkyl
amidopropylamines, alkyl imidazoline derivatives, quaternised amine
ethoxylates, and
quaternary ammonium compounds or nonionic surfactants such as amine oxides,
ether amine
derivatives, ethoxylated alkanolamides, fatty acid alkanolamides. In one
embodiment, the
amine surfactant is tallow amine. In one aspect, the ether amine is selected
from alkoxylated
tertiary ether amine, alkoxylated and non-alkoxylated quaternary etheramine,
and
alkoxylated etheramine oxide.As used herein, the term "non-ionic surfactant"
means a
surfactant which does not have a positive or negative charge, including but
not limited to
alkyl polyoxyethylene ether, polyoxypropylene glycol, an alkyl phenol
ethoxylate, an alcohol
ethoxylate, a sugar ether, a glucoside alkyl ether, a sucrose ester, a
sorbitan ester ethoxylate, a
crop oil concentrate, morpholine amide and a block copolymer. The term "amine
surfactant".
"amine polymer" and "polymer" are used interchangeably herein. The term -amine
surfactant" does not include urea.
[0038] As used herein, the term "cationic emulsifier" means an emulsifier
which has
a positive charge, including but not limited to primary, secondary and
tertiary amines and
salts thereof, alkyltrimethylammonium salts, dialkyldimethylammonium salts,
trialkylmethylammonium salts, tetraalkylammonium salts, alkoxylated
alkylammonium salts,
ester quats, diamidoamine quats, alkyloxyalkyl quats, quaternary
alkylphosphonium salts,
tertiary alkylsulfonium salts, alkylimidazolium salts, alkyloxazolinium salts,
alkylpyridium
salts and N.N-dialkylmorpholinium salts; the cationic emulsifier may comprise
chloride,
bromide, methyl sulfate, sulfate or the like as counterion.
[0039] As used herein, the term "anionic emulsifier" means an emulsifier
which has a
negative charge, including but not limited to alkyl sulfates, arylsulfonates,
fatty alcohol
sulfates, alkylsulfonates, paraffinsulfonates, alkyl ether sulfates, alkyl
polyglycol ether
sulfates, fatty alcohol ether sulfates, alkylbenzenesulfonates (e.g.
dodecylbenzene sulfonate),
12
alkylnaphthylsulfonates, alkylphenyl ether sulfates, alkyl phosphates,
phosphoric acid mono-,
di-, and tri-esters, alkyl ether phosphates, ethoxylated fatty alcohol
phosphoric esters,
alkylphenyl ether phosphates, phosphonic esters, sulfosuccinic diesters,
sulfosuccinic
monoesters, ethoxylated sulfosuccinic monoesters, sulfosuccinamides, a-
olefinsulfonates,
alkyl carboxylates, alkyl ether carboxylates, alkyl polyglycol carboxylates,
fatty acid
isethionate, fatty acid methyltauride, fatty acid sarcoside, arylsulfonates,
naphthalenesulfonates, alkyl glyceryl ether sulfonates, sulfated oils,
polyacrylates and/or cc-
sulfa fatty acid esters. The anionic emulsifier may comprise, for example,
sodium, potassium,
ammonium, monoethanolammonium, triethanolammonium or other organically
substituted
ammonium cations as counterion.
[0040] As used herein, the term "non-ionic emulsifier" means an
emulsifier which
does not have a positive or negative charge, including but not limited to
alcohols, alcohol
ethoxylates, polyoxyethylene-polyoxypropylene-alkyl ethers, amine alkoxylates,
fatty alcohol
polyglycol ethers, fatty amine polyglycol ethers, fatty acid ethoxylates,
fatty acid polyglycol
esters, glyceride monoalkoxylates, alkanolamides, fatty acid alkanolamides,
ethoxylated
alkanolamides, ethoxylated esters, fatty acid alkylolamido ethoxylates,
ethylene oxide-
propylene oxide block copolymers, alkylphenol ethoxylates, alkyl glucosides,
partial esters of
aliphatic carboxylic acids with polyfunctional alcohols, polyethoxylated
polystyrene phenyl
ethers, amides of aliphatic carboxylic acids with alkanolamines, ethoxylated
amides of
aliphatic carboxylic acids with alkanolamines, morpholine amide and
polyalkoxylated
organopoly-siloxanes.
[0041] As used herein, the term "surfactant" means any compound that
lowers the
surface tension of a liquid, the interfacial tension between two liquids or
the tension between
a liquid and a solid.
[0042] As used herein, the term "vaporization" refers to a conversion
in the state of
matter from a liquid to a vapor. "Increased vaporization" refers to conversion
of more liquid
to vapor. "Decreased vaporization" or "reduced vaporization" refers to
conversion of less
liquid to vapor. The term "volatility" refers to the tendency of a liquid to
turn into a vapor.
As used herein, "decreased volatility" and "reduced volatility" is used
synonymously with
"decreased vaporization" and "reduced vaporization". As used herein,
"increased volatility"
is used synonymously with "increased vaporization".
[0043] As used herein, the term "water conditioning" means the property
of
increasing the solubility of a bioactive material, e.g. an herbicide, in water
and/or binding to
ions in water, including but not limited to cations in hard water.
13
Date Recue/Date Received 2020-05-19
[0044] Applicant herein discloses AMS replacement adjuvants and methods
for
producing agricultural spray compositions containing herbicides which do not
increase or
effectively reduce the vaporization of the herbicides. Applicant further
discloses AMS
replacement adjuvants and methods for producing agricultural spray
compositions containing
herbicides which do not increase or effectively reduce the vaporization of the
herbicides and
which also reduce spray drift.
[0045] Applicant herein discloses combination water conditioning
adjuvant and drift
reduction compositions which reduce the problem of spray drift by providing at
least one
component that increases droplet size and at least one adjuvant component
which improves
the efficacy of agricultural spray solutions under hard water conditions.
[0046] Generally, when a farmer desires to spray a bioactive material,
including but
not limited to a post-emergence herbicide such as glyphosate, under hard water
conditions,
the farmer needs to add a water conditioning adjuvant which binds to the ions
in hard water.
If no water conditioning adjuvant is added, then the ions in hard water tend
to bind to the
bioactive material substantially reducing efficacy. The most common water
conditioning
adjuvant used is ammonium sulfate (AMS). Approximately 17 pounds of dry AMS
are
added and mixed for each 100 gallons of carrier water used for spraying
bioactive materials.
AMS is bulky and inconvenient for a farmer to use. Applicant has disclosed in
U.S. Patent
Application Publication No. 2005/0026780 that a mineral acid, for example
sulfuric acid, can
be formulated as a water conditioning adjuvant when combined with an amine
surfactant,
such as tallow amine, providing water conditioning adjuvant properties which
are equal to or
superior to AMS.
[0047] Additionally, when a farmer desires to spray a bioactive
material, the farmer
generally needs to reduce the drift of the bioactive material outside of the
target area of
application. Among the most commonly used drift reduction agents is lecithin
(e.g. soy
lecithin) which serves to increase the droplet size of the sprayed bioactive
material. Drift
reduction agents used by farmers include phospholipids, vegetable colloids,
non-derivatized
guar gum, non-cationic derivatized guar gum, cationic guar gum, polyethylene
oxides, poly
(vinyl pyrrolidones), polyacrylamides, a non-ionic emulsifier, a cationic
emulsifier and an
anionic emulsifier. Generally, the drift reduction agent is a separate
composition, carried in a
container separate from the water conditioning adjuvant that a farmer must add
to carrier
water in addition to the water conditioning adjuvant.
[0048] Furthermore, farmers are facing negative impacts to crop yields
from the
development in pest species of resistance to commonly used herbicides such as
glyphosate.
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Agricultural companies are trying to address this problem for farmers by
providing corn,
soybean and cotton varieties with combinations of herbicide resistance traits.
In particular,
varieties are being developed that have resistance to glyphosate and either
2,4-D or dicamba.
A major problem facing the industry is that certain adjuvants used for water
conditioning
increase the vaporization of herbicides, including 2,4-D and dicamba. In one
aspect,
increased vaporization means that instead of the liquid herbicide contacting
the plant where it
can perform its herbicidal function, the herbicide turns into vapor and
herbicidal efficacy is
lost. In addition, increased vaporization can cause increased spray drift
which can cause
damage to sensitive off target crops. Therefore there is a need for water
conditioning
adjuvants and methods for preparing agricultural sprays which either do not
increase
vaporization of herbicides or reduce the vaporization of herbicides.
[0049] Applicant has found that commonly used AMS replacement adjuvants,
including HEL-FIRE and BRIMESTONE substantially increase the vaporization of
dicamba
and 2,4-D herbicides, see Figures 3-5. Both HEL-FIRE and BRIMESTONE contain a
combination of urea and sulfuric acid.
[0050] Applicant has developed compositions and methods for conditioning
water in
an agricultural herbicidal spray composition while not increasing or
effectively reducing the
vaporization of the herbicides. In particular, Applicant has found that
combining an amine
surfactant with a mineral acid does not increase or reduces the volatility of
bioactive
materials while providing water conditioning. More specifically, in one
aspect, Applicant has
found that combining polyamines with sulfuric acid reduces volatility of
herbicides. Thus,
compositions and methods are provided for improving herbicidal efficacy by,
among other
mechanisms, binding to the ions in hard water and minimizing loss of
herbicidal efficacy
from herbicide vapor formation.
[0051] Applicant has developed a composition and process of making said
composition which combines a water conditioning adjuvant with a drift
reduction agent into
one combination composition contained in a single container. The combination
water
conditioning adjuvant and drift reduction composition provides a high level of
convenience to
the farmer such that the single combined composition provides the benefits of
both water
conditioning adjuvant and drift reduction. Further, the combination water
conditioning
adjuvant and drift reduction composition disclosed herein provides water
conditioning
adjuvant properties and drift reduction as effective as or superior to
commercial standards.
[0052] Applicant has further developed compositions and methods for
conditioning
water and providing drift reduction in an agricultural herbicidal spray
composition while not
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increasing or effectively reducing the vaporization of the herbicides. Thus,
means are
provided for improving herbicidal efficacy by, among other mechanisms, binding
to the ions
in hard water and providing for drift reduction and minimizing loss of
herbicidal efficacy
from herbicide vapor formation.
[0053] A concentrated mineral acid, such as sulfuric acid, can react
adversely with
organic compounds, such as phospholipids, forming undesirable by-products, see
Example 1.
Applicant has surprisingly shown that a concentrated mineral acid, such as
sulfuric acid, can
be maintained in combination with organic drift reduction compounds, such as
phospholipids,
without reactions resulting in undesirable by-products, if an amine surfactant
is used to
stabilize the combination, see Example 1. This surprising result has been
achieved, in one
embodiment, by providing for the amine surfactant tallow amine in equal or
greater
concentration than the concentration of the sulfuric acid before the addition
of phospholipids
(e.g. lecithin). This result is particularly surprising because in the
presence of some amine
compounds which are not surfactants (e.g. urea), a concentrated mineral acid
(e.g. sulfuric
acid) reacts adversely with an organic drift reduction compound (e.g.
lecithin) resulting in a
cloudy suspension and separation of liquid components, see Example 1.
[0054] Applicant has further found that the introduction of excessive water
into the
combination water conditioning adjuvant and drift reduction composition
results in adverse
reaction between the mineral acid and the drift reduction agent. One means by
which water
is minimized in one embodiment of the combination water conditioning and drift
reduction
composition disclosed herein is by use of concentrated mineral acid which
itself has a low
water content.
[0055] Applicant has also found that when the combination water
conditioning
adjuvant and drift reduction composition is introduced into carrier water,
e.g. 100 gallon tank,
for agricultural spray application, the mineral acid does not adversely react
with the drift
reduction agent due to the large scale of dilution.
[0056] In one embodiment, a composition for agricultural use is disclosed
comprising
a water conditioning adjuvant comprising a concentrated mineral acid and an
amine
surfactant; and a drift reduction agent selected from the group consisting of
at least one
phospholipid, vegetable colloids, non-derivatized guar gum, non-cationic
derivatized guar
gum, cationic guar gum, polyethylene oxides, poly (vinyl pyrrolidones),
polyacrylamides, a
non-ionic emulsifier, a cationic emulsifier which is not an amine surfactant,
and an anionic
emulsifier. In some embodiments, the drift reduction agent is at least one
phospholipid
selected from the group consisting of lecithin, phosphatidic acid,
phosphotidyl ethanolamine,
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phosphatidylcholine, phosphatidylserine, phosphatidylinositol,
phosphatidylinositol
phosphate, phosphatidylinositol biphosphate, phosphatidylinositol
triphosphate, and mixtures
thereof. In some embodiments, the concentrated mineral acid can be selected
from the group
consisting of sulfuric acid, perchloric acid, hydroiodic acid, hydrobromic
acid, hydrochloric
acid, and nitric acid. In some embodiments, the amine surfactant can be
selected from the
group consisting of octyl amine, lauryl amine, stearyl amine, oleyl amine,
tallow amine,
cetylamine, N-tetradecyl amine, cocoamine, hydrogenated tallow amine,
di(hydrogenated)
tallow amine, dicocoalkyl amine, N-tridecyltridecanamine, N-
methylstearylamine, distearyl
amine, ether amine and dialkyl (C8-C20) amine. In one aspect, the
concentration of tallow
amine can be equal to or greater than the concentration of sulfuric acid in
the composition.
Embodiments include the composition further comprising an oil selected from
the group
consisting of free fatty acids, mineral oil, vegetable oil, methylated seed
oil, ethylated seed
oil, butylated seed oil, and mixtures thereof. Embodiments include the
composition
comprising an oil selected from soybean oil, sunflower oil, cotton seed oil,
crop oil
concentrate and methylated soybean oil. Embodiments further include the
composition
comprising a glycol selected from the group consisting of diethylene glycol,
triethylene
glycol, tetraethylene glycol and pentaethylene glycol. Embodiments also
include the
composition comprising a non-ionic surfactant selected from the group
consisting of an alkyl
polyoxyethylene ether. polyoxypropylene glycol, an alkyl phenol ethoxylate, an
alcohol
ethoxylate, a sugar ether, a glucoside alkyl ether, a sucrose ester, a
sorbitan ester ethoxylate, a
crop oil concentrate, morpholine amide and a block copolymer. In one aspect,
the sugar ether
is selected from the group consisting of glucoside alkyl ether, xylose alkyl
ether, arabinose
alkyl ether, mannose alkyl ether, ribose alkyl ether, rhamnose alkyl ether,
galactose alkyl
ether, sucrose alkyl ether, maltose alkyl ether, lactose alkyl ether, fructose
alkyl ether, and
raffinose alkyl ether. In one aspect, the alkyl group has 8 to 20 carbon
atoms. In another
aspect, the alky group has 10 to 18 carbon atoms. In one aspect, the
surfactant is Isoclear 55.
In one aspect, the composition does not contain and is not contacted with
ammonium sulfate
(AMS). Embodiments include the composition comprising an emulsifier and/or an
additive
selected from a buffering agent, a defoaming agent, a wetting agent, a
sticking agent and a
tank cleaner. In one aspect, the water content of the composition is below 5 %
(v/v), before
dilution of the composition in carrier water. In another aspect, the water
content of the
composition is below 1 % (v/v), before dilution of the composition in carrier
water.
Embodiments of the invention include a composition comprising 1-25% by weight
or volume
concentrated mineral acid, 10-50% by weight or volume amine surfactant. 10-60%
by weight
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or volume phospholipid. 10-50% by weight or volume oil and 5-50% by weight or
volume
glycol. Embodiments of the invention further include a composition comprising
1-25% by
weight or volume concentrated sulfuric acid, 10-50% by weight or volume tallow
amine, 10-
60% by weight or volume lecithin, 10-50% by weight or volume methylated seed
oil and 5-
50% by weight or volume diethylene glycol.
[0057] In one aspect, the fatty acid is selected from the group consisting
of free C12-
C18 fatty acid, CAS No. 67762-38-3 (Fatty acids, C16-18 and C18-unsatd., Me
esters), CAS
No. 162627-18-1 (Fatty acids, C18-unsatd., trimers, reaction products with
triethylenetetramine), polyethylene sorbitol C8-C18 fatty acid esters, CAS No.
68553-02-6
(fatty acids, coco, esters with polyethylene glycol ether with glycerol
(3:1)), CAS No. 68424-
50-0 (fatty acids, tall-oil, C12-15-alkyl esters, sulfated, sodium salts), and
CAS No. 61790-
90-7 (fatty acids, tall-oil, hexaesters with sorbitol, ethoxylated). In
another aspect, the fatty
acid is CAS No. 67701-08-0 (fatty acid. C16-C18 and C18-unsatd).
[0058] The present application also discloses a process of preparing a
composition for
agricultural use comprising adding a concentrated mineral acid to an amine
surfactant to
obtain a water conditioning adjuvant; and adding the water conditioning
adjuvant to a drift
reduction agent selected from the group consisting of at least one
phospholipid, vegetable
colloids, non-derivatized guar gum, non-cationic derivatized guar gum,
cationic guar gum,
polyethylene oxides, poly (vinyl pyrrolidones), polyacrylamides, a non-ionic
emulsifier, a
cationic emulsifier which is not an amine surfactant, and an anionic
emulsifier. In some
embodiments, the process comprises a drift reduction agent that is at least
one phospholipid
selected from the group consisting of lecithin, phosphatidic acid,
phosphotidyl ethanolamine,
phosphatidylcholine, phosphatidylserine, phosphatidylinositol,
phosphatidylinositol
phosphate, phosphatidylinositol biphosphate, phosphatidylinositol
triphosphate, and mixtures
thereof. In some embodiments, the concentrated mineral acid of the process can
be selected
from the group consisting of sulfuric acid, perchloric acid, hydroiodic acid,
hydrobromic
acid, hydrochloric acid, and nitric acid. Embodiments of the process include
an amine
surfactant selected from the group consisting of octyl amine, lauryl amine,
stearyl amine,
ley' amine, tallow amine, cetylamine, N-tetradecyl amine, cocoamine,
hydrogenated tallow
amine, di(hydrogenated) tallow amine, dicocoalkyl amine, N-
tridecyltridecanamine, N-
methylstearylamine, distearyl amine, ether amine and dialkyl (C8-C20) amine.
In one aspect,
the concentration of tallow amine used in the process can be equal to or
greater than the
concentration of sulfuric acid in the composition. In some embodiments, the
process
comprises addition of an oil selected from the group consisting of free fatty
acids, mineral oil,
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vegetable oil, methylated seed oil, ethylated seed oil, butylated seed oil,
and mixtures thereof.
Embodiments of the process include addition of an oil selected from soybean
oil, sunflower
oil, cotton seed oil, crop oil concentrate and methylated soybean oil. In some
embodiments,
the process comprises addition of a glycol selected from the group consisting
of diethylene
glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.
Embodiments of the
process also include addition of a non-ionic surfactant selected from the
group consisting of
an alkyl polyoxyethylene ether, polyoxypropylene glycol, an alkyl phenol
ethoxylate, an
alcohol ethoxylate, a sugar ether, a glucoside alkyl ether, a sucrose ester, a
sorbitan ester
ethoxylate, a crop oil concentrate, morpholine amide and a block copolymer. In
one aspect,
the process does not add ammonium sulfate (AMS) to the composition or contact
the
composition with AMS. Some embodiments of the process comprise adding an
emulsifier
and/or an additive selected from a buffering agent, a defoaming agent, a
wetting agent, a
sticking agent and a tank cleaner. In one embodiment of the process, the water
content of the
composition is below 5 % (v/v), before dilution of the composition in carrier
water.
Embodiment of the process include, the water content of the composition is
below 1 % (v/v),
before dilution of the composition in carrier water.
[0059] The
present application further discloses a product resulting from a specified
process wherein a composition is prepared by a process comprising adding a
concentrated
mineral acid to an amine surfactant to obtain a water conditioning adjuvant;
and adding the
water conditioning adjuvant to a drift reduction agent selected from the group
consisting of at
least one phospholipid, vegetable colloids, non-derivatized guar gum, non-
cationic
derivatized guar gum, cationic guar gum, polyethylene oxides, poly (vinyl
pyrrolidones),
polyacrylamides, a non-ionic emulsifier, a cationic emulsifier which is not an
amine
surfactant, and an anionic emulsifier. In some embodiments of the product, the
process
comprises a drift reduction agent selected to be at least one phospholipid
selected from the
group consisting of lecithin, phosphatidic acid, phosphotidyl ethanolamine,
phosphatidylcholine, phosphatidylserine, phosphatidylinositol,
phosphatidylinositol
phosphate, phosphatidylinositol biphosphate, phosphatidylinositol
triphosphate, and mixtures
thereof. In some embodiments of the product, the process comprises
concentrated mineral
acid selected from the group consisting of sulfuric acid, perchloric acid,
hydroiodic acid,
hydrobromic acid, hydrochloric acid, and nitric acid. In some embodiments of
the product,
the process comprises amine surfactant selected from the group consisting of
octyl amine,
lauryl amine, stearyl amine, ()ley' amine, tallow amine, cetylamine, N-
tetradecyl amine,
cocoamine, hydrogenated tallow amine, di(hydrogenated) tallow amine,
dicocoalkyl amine,
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N-tridecyltridecanamine, N-methylstearylamine, distearyl amine, ether amine
and dialkyl
(C8-C20) amine. In one aspect, the concentration of tallow amine can be equal
to or greater
than the concentration of sulfuric acid in the composition. Embodiments of the
product result
from a process comprising addition of an oil selected from the group
consisting of free fatty
acids, mineral oil, vegetable oil, methylated seed oil, ethylated seed oil,
butylated seed oil,
and mixtures thereof. Some embodiments of the product result from a process
which
comprises addition of an oil selected from soybean oil, sunflower oil, cotton
seed oil, crop oil
concentrate and methylated soybean oil. Embodiments of the product further
include the
result of a process comprising addition of a glycol selected from the group
consisting of
diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene
glycol.
Embodiments of the product also include the result of a process comprising
addition of a non-
ionic surfactant selected from the group consisting of an alkyl
polyoxyethylene ether,
polyoxypropylene glycol, an alkyl phenol ethoxylate, an alcohol ethoxylate, a
sugar ether, a
glucoside alkyl ether, a sucrose ester, a sorbitan ester ethoxylate, a crop
oil concentrate,
morpholine amide and a block copolymer. In one aspect, the composition does
not contain
and is not contacted with ammonium sulfate (AMS). Embodiments of the product
include
the results of a process comprising addition of an emulsifier and/or an
additive selected from
a buffering agent, a defoaming agent, a wetting agent, a sticking agent and a
tank cleaner. In
one aspect, the water content of the composition is below 5 % (v/v), before
dilution of the
composition in carrier water. In another aspect, the water content of the
composition is
below 1 % (v/v), before dilution of the composition in carrier water.
[00601 The present application also discloses a method for reducing drift
during
release of an aqueous composition suitable for treating agricultural acreage
comprising the
steps of: forming the aqueous composition suitable for treating agricultural
acreage by mixing
a composition for agricultural use (comprising a water conditioning adjuvant
comprising a
concentrated mineral acid and an amine surfactant; and a drift reduction agent
selected from
the group consisting of at least one phospholipid, vegetable colloids, non-
derivatized guar
gum, non-cationic derivatized guar gum, cationic guar gum, polyethylene
oxides, poly (vinyl
pyrrolidones), polyacrylamides, a non-ionic emulsifier, a cationic emulsifier
which is not an
amine surfactant, and an anionic emulsifier), carrier water and a bioactive
material; and
spraying the aqueous composition on agricultural acreage; wherein the
composition is about
0.25 % (v/v) to about 5 % (v/v) of the aqueous composition. Embodiments of the
method for
reducing spray drift include selection of the bioactive material from the
group consisting of
pesticides, herbicides, fungicides, insecticides, acaricides, nematocides,
foliar nutrients,
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defoliants, plant growth regulators, and molluscicides. Embodiments of the
method for
reducing spray drift also include selection of the bioactive material from the
group consisting
of glyphosate (N-(phosphonomethyl)glycine) and dicamba.
[0061] In one embodiment, the mineral acid is sulfuric acid, including but
not limited
to concentrated sulfuric acid which is at least 93% concentrated sulfuric
acid. In another
embodiment, the sulfuric acid is at least 98% concentrated sulfuric acid. In
other
embodiments, mineral acids such as concentrated perchloric acid, hydroiodic
acid,
hydrobromic acid, hydrochloric acid, and nitric acid can be used. The mineral
acid may be
used in amounts of between about 1% and about 50% (weight: weight or volume:
volume)
in the water conditioning adjuvant composition. In some embodiments the amount
is
between about 1% and about 25%. In other embodiments, the amount of mineral
acid may be
about 1%, about 2%, about 3%, about 4%, about 5%, about 6%. about 7%, about
8%, about
9%, about 10%, about 12%, about 13%. about 14%. about 15%, about 16%, about
17%,
about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%,
or about
25% of the water conditioning adjuvant composition.
[0062] An amine surfactant may be used in amounts of between about 10% and
about
50% (weight : weight or volume : volume) in the water conditioning adjuvant
composition
and/or the drift reduction composition. In some embodiments, the amount of
amine
surfactant may be about 20%, about 22%, about 24%, about 26%, about 28%, about
30%,
about 32%, about 34%, about 36%, about 38%, about 40%, about 42%, about 44%,
about
46%, about 48%, or about 50% (weight : weight or volume : volume) of the water
conditioning adjuvant composition, drift reduction composition, or combination
composition
comprising both water conditioning adjuvant and drift reduction agent. In some
embodiments, the amount of amine surfactant is less than or equal to 20%, is
less than or
equal to 22%, is less than or equal to 24%, is less than or equal to 26%, is
less than or equal
to 28%, is less than or equal to 30%, is less than or equal to 32%, is less
than or equal to 34%,
is less than or equal to 36%, is less than or equal to 38%, is less than or
equal to 40%, is less
than or equal to 42%, is less than or equal to 44%, is less than or equal to
46%, is less than or
equal to 48%, or is less than or equal to 50% (weight : weight or volume:
volume) of the
water conditioning adjuvant composition, drift reduction composition, or
combination
composition comprising both water conditioning adjuvant and drift reduction
agent. In one
embodiment, the amount of amine surfactant is greater than or equal to the
amount of mineral
acid (weight: weight or volume: volume).
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[0063] The water conditioning adjuvant composition and/or the drift
reduction agent
optionally comprise an emulsifier which may serve to prevent separation of
tallow amine
from the mixture or otherwise improve the effectiveness or usability of the
composition.
[0064] The water conditioning adjuvant composition optionally further
comprises a
glycol. Such glycols include diethylene glycol (DEG), triethylene glycol,
tetraethylene
glycol and pentaethylene glycol. Glycol can be added in an amount of between
5% and about
50% and up. Glycol can be added to the compositions in divided amounts, for
example,
about 5% to about 50% added prior to the addition of the mineral acid and/or
the amine
surfactant, followed by the remainder of the glycol. Among other benefits,
glycol provides
flowability to the composition.
[0065] Exemplary drift reduction agents comprising phospholipids include
commercially available lecithin-containing drift reduction agents such as
SOLEC 3F-UB,
LIBERATE, LI 700, AIRLINK, ACTIFY, COMPADRE, FIRST CHOICE ALPHA APS,
FRANCHISE, MONTEREY SUPER 7, MS0 CONCENTRATE WITH LECI-TECH, PHT
AD-BUFF, POLYTEX L525, PROLEC, SYNTHEX GL, TORPEDO, TRANSMIT, 3F-UB;
TURFGO PROFESSIONAL TURF PRODUCTS LI 700, VADER, WEATHER GARD
COMPLETE, AF 1; AF 1 (lecithin); ACTI-FLOW 685B; ADLEC; ALCOLEC BS;
ALCOLEC F 100; ALCOLEC PC 75; ALCOLEC PG; ALCOLEC S; ALCOLEC Z 7;
BASIS LP 2070R; BASIS LP20B; BENECOAT BMI 40; BIO BLATT
MEHLTAUMITTEL; BIOBLATT; CENTIOCAP 162U5; CENTREX F; CENTROL 3F-UB;
CENTROL 3FSB; CENTROLEX R; CENTROPHASE HR 2B; CENTROPHILL IP;
CETINOL;E 322;E 322 (EMULSIFIER); EMULFLUID E; EMULMETIK 100;
EMULSIFIER L; EMULTHIN M 35; GLIDDEX; GRANULESTIN; KELECIN; L 0023;
LECI PS20P; LECI-PC 35P; LECIGRAN1000P; LECION; LECION P; LECIPRIME 1500;
LECIPRIME1800IP; LECITH1NE; LECITHINON; LECITHOL;LECIWET WD 120;
LIPOID S 45; LIPOTIN100UB; LIPOTIN NE; METARIN P; PHOSPHOLIPIDS,
LECITHIN COM. PREPNS.; PHOSPHOLIPON 85G; PHOSPHOLUTEIN; PLANTICIN;
SICO-NS;SLP-PI POWDER; STERNPRIMEN 10 TOP; SUNLECITHIN L 6; TINODERM
P; TOPCITIN 50; TROYKYD LECITHIN WD; ULTRALEC; VAMOTHIN SBX; YELKIN
SS; YELKIN TS; and YELKIN TTS. The principal quality parameters for commercial
lecithins are: phospholipid content (measured as percent acetone insolubles),
free acidity,
non-lipid impurities (measured as hexane insolubles), viscosity and color.
Alternatively, the
phospholipid containing drift reduction agent may be prepared without use of a
commercially
available lecithin-containing product. In some embodiments of the compositions
disclosed
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herein, the phospholipid containing drift reduction agent includes liquid
lecithins such as
soybean based lecithins comprising mixtures of acetone insolubles, oils, and
water. In some
embodiments, the acetone insolubles may comprise 60% to 65% by weight, or
about 62% by
weight of the lecithin. The acetone insolubles in the lecithin may comprise
carbohydrates and
polar lipids such as phospholipids and glycolipids. In some embodiments, the
phospholipids
are selected from the group consisting of phosphatidylcholines,
phosphatidylethanolamines,
phosphatidylserines and phosphatidylinositols.
[0066] The phospholipid component of the drift reduction agent may be used
in
amounts of between about 10% and about 60% (weight: weight or volume : volume)
of the
drift reduction agent or of the combination water conditioning adjuvant and
drift reduction
agent. In some embodiments, the phospholipid component may be about 20%, about
22%,
about 24%, about 26%, about 28%, about 30%, about 32%, about 34%, about 36%,
about
38%, about 40%, about 42%, about 44%, about 46%, about 48%, about 50%, about
52%,
about 54%, about 56%, about 58% or about 60% (weight : weight or volume:
volume) of the
drift reduction agent or of the combination composition comprising both water
conditioning
adjuvant and drift reduction agent. In some embodiments, the phospholipid
component is
less than or equal to 20%, is less than or equal to 22%, is less than or equal
to 24%, is less
than or equal to 26%, is less than or equal to 28%, is less than or equal to
30%, is less than or
equal to 32%, is less than or equal to 34%, is less than or equal to 36%, is
less than or equal
to 38%, is less than or equal to 40%, is less than or equal to 42%, is less
than or equal to 44%,
is less than or equal to 46%, is less than or equal to 48%, or is less than or
equal to 50%, less
than or equal to 52%, less than or equal to 54%, less than or equal to 56%,
less than or equal
to 58%, or less than or equal to 60% (weight: weight or volume : volume) of
the drift
reduction agent or combination composition comprising both water conditioning
adjuvant
and drift reduction agent.
[0067] In some embodiments the optional oils of the drift reduction agent
comprise
10-50% by weight, or 34% to 40% by weight. or 36% to 38% by weight, and in
some
embodiments water comprises about 5% or less by weight, and in some
embodiments water
comprises about 1% or less by weight of the combination composition comprising
water
conditioning adjuvant and drift reduction agent or of the drift reduction
agent. In one
embodiment the oil comprises methyl esters such as methyl soyate.
[0068] The oils can comprise neutral lipids such as triglycerides,
including but not
limited to soybean oil. In one embodiment, the oil is methylated seed oil
(MS0). Other
embodiments include other oils such as mineral oil, vegetable oil, ethylated
seed oil,
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butylated seed oil, soybean oil, sunflower oil, cotton seed oil, crop oil
concentrate and
methylated soybean oil.
[0069] The oil component is optionally included in the drift reduction
agents of the
present invention to make the phospholipid mixture less viscous and easier to
pump and stir
during the spraying process. The drift reduction agent of the present
invention optionally
includes a non-ionic surfactant to allow the drift reduction agent to more
easily dissolve into
aqueous solutions and form aqueous spray compositions.
[0070] The drift reduction agent may also further comprise a surfactant. In
addition
to any other surfactants mentioned herein, the surfactant can comprise a non-
ionic surfactant
such as polyoxyethylene ether (an ethoxylated alcohol) of the formula
RO(CH,CH,O)0H,
where R is a linear, primary alcohol and n is the number of ethylene oxide
units. In some
embodiments, the non-ionic surfactant is the polyoxyethylene ether, optionally
TOMODOL
1-5, where R is a linear, C1-11 alkyl group and n=5 to make the formula
H13C110(CH2CH20)5 H. Other surfactants such as alkyl polyoxyethylene ethers,
polyoxypropylene glycol, alkyl phenol ethoxylates, alcohol ethoxylates, a
sugar ether,
glucoside alkyl ethers, sucrose esters, sorbitan ester ethoxylates, crop oil
concentrates,
morpholine amide and block copolymers can be used.
[0071] The water conditioning adjuvant of the invention may be mixed with
the drift
reduction agent to result in the combination composition for agricultural use
in any
proportions that will result in effective water conditioning and drift
reduction. In some
embodiments, the water conditioning adjuvant can comprise between about 25%
and about
75% of the final composition, with the drift reduction agent comprising
between about 75%
and about 25%, respectively. It is noted that the adjuvant composition for
agricultural use
can then be further diluted with, e.g. carrier water, bioactive agents, and
the like, in which
case the proportion of each component, e.g. the water conditioning adjuvant
and the drift
reduction agent, will proportionally be reduced in the diluted composition for
agricultural
use.
[0072] The adjuvant compositions for agricultural use may further comprise
(e.g., be
mixed with) water and/or bioactive materials such as pesticides, herbicides,
fungicides,
insecticides, acaricides, nematocides, foliar nutrients, defoliants, plant
growth regulators, and
molluscicides.
[0073] The Water Quality Association of the United States defines hard
water as
having dissolved mineral hardness of 1 GPG (grain per gallon) or more.
Definitions of
hardness of water: Soft Water- less than 1 gpg; Slightly Hard- 1-3.5 gpg;
Moderately Hard-
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3.5-7 gpg; Very Hard- 7-10 gpg; Extremely Hard- over 10 gpg. Carrier water for
the spray
solutions of the present invention may include any of these water hardness
types as described
above. The adjuvant compositions are especially suitable for use with hard
water to
minimize disadvantages arising from use of hard water. Water in the spray
mixture may be
of any ratio as is known in the art, in some instances may be between 0.25%
and 5% by
volume of combination composition for agricultural use.
[0074] The herbicides are optionally selected from the group consisting of
glyphosate
(N-phosphonomethylglycine), acifluorfen (5-(2-chloro-4-
(trifluoromethyl)phenoxy)-2-
nitrobenzoic acid), chloramben (3-amino-2,5-dichlorobenzoic acid), 2,4-D ((2,4-
dichlorophenoxylacetic acid), endothal (7-oxabicyclo(2.2.1)heptane-2,3-
dicarboxylic acid),
mecoprop (2-(2-methyl-4-chlorophenoxy)propionic acid), picloram (4-amino-3,5,6-
trichloropyridine-2-carboxylic acid), 2,4,5-T((2,4,5-trichlorophenoxy)acetic
acid), benzac
(2,3,6-trichlorobenzoic acid), dicamba (3,6-dichloro-o-anisic acid), MCPA (4-
chloro-o-
tolyloxyacetic acid), dalapon (2.2-dichloropropionic acid), dichlorprop (2-
(2,4-
dichlorophenoxy)propionic acid), MCPB (4-(4-chloro-o-tolyloxy)butyric acid),
bialaphos (L-
2-amino-4-((hydroxy)(methyl)phosphinoyl)butyryl-L-alanyl-L-alanine),
glufosinate ((3-
amino-3-carboxypropyl)methylphosphinate), imazethapyr (2- { 4,5-dihydro-4-
methy1-4-(1-
methylethyl)-5-oxo-1H-imidazol-2-y11-5-ethyl -3-pyridinecarboxylic acid),
imazaquin (2-
{4,5-dihydro-4-methy1-4-(1-methylethyl)-5-oxo-1H-imidazol-2-y1}-3-quino
linecarboxylic
acid), and mixtures thereof. In some embodiments the herbicide is an
isopropylamine and/or
potassium salt of glycophosate or other salts of glyphosate or glufosinate
(e.g., ROUNDUP
ULTRAMAX or ROUNDUP WEATHERMAX from Monsanto Company or other
suppliers), and may be mixed in with the adjuvant suitable for agricultural
use in any art-
known and suitable amount, as directed by the manufacturer.
[0075] The compositions of the present invention also optionally include
one or more
compositions selected from the group consisting of buffering agents, defoaming
agents,
wetting agents, sticking agents, and tank cleaners.
[0076] Applicant has further developed agricultural spray adjuvants for
hard water
conditions which do not increase or effectively reduce the vaporization of
herbicides. The
present application further discloses methods for preparing agricultural spray
adjuvants for
hard water conditions which do not increase or effectively reduce the
vaporization of
herbicides. In particular, Applicant has found that combining an amine
surfactant with a
mineral acid does not increase or reduces the volatility of bioactive
materials while providing
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water conditioning. More specifically, in one aspect, Applicant has found that
combining
polyamines with sulfuric acid reduces volatility of herbicides.
[0077] As noted above, many adjuvants increase the vaporization of
herbicides, such
as dicamba and 2,4-D. The increase in vaporization can increase the drift of
the herbicides
which could cause damage to sensitive off-target crops in nearby fields. In
addition, the
increase in vaporization makes the herbicides less effective on target pests
because a
substantial portion of the herbicide evaporates.
[0078] Tables 12-14 of this application disclose water conditioning
adjuvants which
as described at Example 15 provide water conditioning which improves
herbicidal efficacy
and do not increase or effectively reduce the vaporization of herbicides. The
property of non-
increased or decreased vaporization is compared to competitor products in
Figures 3-4. As
seen from Figures 3-4, competitor adjuvant products NEL-FIRE and BRIMESTONE
(both
contain urea in combination with sulfuric acid) substantially increased
dicamba vaporization
compared to the Load Out composition specified in Table 12. Example 15 also
discloses a
method for producing an agricultural spray solution comprising an herbicide
which provides
water conditioning while not increasing or decreasing the vaporization of the
herbicide. A
method for providing water conditioning while not increasing or decreasing the
vaporization
of the herbicide comprises preparation of a water conditioning adjuvant by
adding strong
mineral acids to polymers, such as tallow amine, which are then combined with
an herbicide
such as dicamba or 2,4-D. Figure 6 illustrates the reduction in volatility of
2,4-D provided by
Load Out in comparison to AMS. In one embodiment of the method for providing
water
conditioning while not increasing or decreasing the vaporization of the
herbicide, the acid and
polymer are combined as in Table 12. The composition of Table 12 may be added
in a ratio
of 1 quart to 2 gallons of adjuvant to 100 gallons of spray solution
containing herbicide.
[0079] Figure 5 illustrates how Full Load Complete, disclosed elsewhere
herein as
AQ 284, does not increase or effectively reduces the vaporization of the
herbicide 2,4-D in
comparison to competitor products. As seen from Figure 5, competitor adjuvant
products
HEL-FIRE and BRIMESTONE (which both contain urea in combination with sulfuric
acid)
either decreased vaporization of 2,4-D less than Full Load Complete
(BRIMESTONE) or
increased vaporization of 2,4-D (HEL-FIRE). AQ 284 may be added from 0.25 %
(v/v) to 5
% (v/v) of the spray solution comprising the herbicide.
EXAMPLES
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[0080] The following examples are provided for illustrative purposes only
and are not
intended to limit the scope of the invention as defined by the appended
claims. All examples
described herein should be considered in the context of standard techniques,
which are well
known and routine to those of skill in the art.
Example 1. Lecithin Stability in AQ 216 Mixture Containing Sulfuric Acid and
Tallow
Amine
[0081] Lecithin is known to be unstable in a sulfuric acid environment. As
shown in
Table 1, products containing lecithin, such as AIRLINK (UCPA LLC), LIBERATE
(UAP)
and LI700 (UAP) react differently with sulfuric acid, urea sulfate and with a
mixture of
sulfuric acid and tallow amine (AQ 216). For each reaction with urea sulfate
and AQ 216,
the urea sulfate was mixed thoroughly or AQ 216 was mixed thoroughly, before
the addition
of the lecithin composition. The results of Table I show that 50 mL of each of
the referenced
lecithin compositions reacted adversely with 3 mL of sulfuric acid, forming a
precipitate; 50
mL of each of the lecithin compositions reacted adversely with urea sulfate
comprising an
equivalent amount of sulfuric acid, forming a gel; whereas 50 mL of each of
the lecithin
compositions did not react adversely with AQ 216 comprising an equivalent
amount of
sulfuric acid, maintaining a clear solution for 12 hours and longer (data not
shown).
Table 1. Results of Lecithin Addition to Sulfuric Acid, Urea Sulfate and AQ
216
Treat- Ratio Lecithin
ment Composition Notes Time 1 hour Time 12 Hours
Sulfuric
Acid 3 mL: 50 mL AIRLINK Dark Precipitate More precipitate More
precipitate
Urea
Sulfate 6 mL : 50 mL AIRLINK Cloudy Cloudy Separate
Gel with separate Liquid
AQ 216 6 mL : 50 mL AIRLINK Clear Clear Clear
Sulfuric
Acid 3 mL: 50 mL LI 700 Dark Precipitate More precipitate More
precipitate
Urea
Sulfate 6 mL: 50 mL LI 700 Cloudy Cloudy Separate Gel with
separate Liquid
AQ 216 6 mL: 50 mL LI 700 Clear Clear Clear
Sulfuric
Acid 3 mL : 50 mL LIBERATE Dark Precipitate More precipitate More
precipitate
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Urea
Sulfate 6 mL: 50 mL LIBERATE Cloudy Cloudy Separate Gel with
separate Liquid
AQ 216 6 mL: 50 mL LIBERATE Clear Clear Clear
Sulfuric Acid: 95% Concentrated
Urea Sulfate: 45% Sulfuric (95% concentrated) + 40% Urea
AQ 216: 48% Sulfuric acid (95% concentrated) + 48% Tallow amine + 4%
Diethylene
glycol (DEG)
[0082] The addition of a pre-mix of sulfuric acid plus tallow amine plus
DEG (AQ
216) to these lecithin containing products did not affect the products in a
negative way. This
is a surprising result as one of ordinary skill in the art would reasonably
expect sulfuric acid
to adversely react with lecithin resulting in undesirable by-products.
Example 2: Process for AQ 284 synthesis:
[0083] The process of making AQ 284 which is a combination water
conditioning
adjuvant and drift reduction composition requires separately preparing AQ 283
which is a
water conditioning adjuvant and AQ 323 which is a drift reduction agent and
then combining
AQ 283 and AQ 323.
[0084] AQ 283 water conditioning adjuvant was prepared by adding the
components
of Table 2 in the order indicated. The components were added at room
temperature and the
composition was mixed to homogeneity after the addition of the component of
each step.
Table 2 provides for the preparation of a 100 lb batch of AQ 283. The final
density of AQ
283 is 9.3679 lbs/ gallon.
Table 2. AQ 283 Water Conditioning Adjuvant
Step Component Weight Weight of Density of Volume of Component
Percent Component Component Added (gallons)
Added (lbs) lbs/gallon
Step DEG 25 25 9.35 2.67
1
Step TC101 0 0 8.4 0.00
2
Step TERWET 45 45 8.5 5.29
3
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Step Sulfuric 12 12 15.35 0.78
4 Acid
Step DEG 18 18 9.35 1.93
The volume of components to be added was determined by dividing the weight of
the
component to be added by the density of said component. DEG, diethylene
glycol, was
added at two different steps first at Step l and then at Step 5. TCl 01 is an
antifoaming agent
added at approximately 0.001 % by weight. TERWET is tallow amine blended with
emulsifier, comprising approximately 78% tallow amine and approximately 22%
emulsifier.
The sulfuric acid used was concentrated 98% sulfuric acid which had a density
just under
15.35 lbs/gallon. The sulfuric acid was added in the amount of 0.78 gallons/
100 lb batch of
AQ 283 as indicated in Table 2.
[0085] AQ 323 drift reduction agent was prepared by adding the components
of Table
3 in the order indicated. The components were added at room temperature and
the
composition was mixed to homogeneity after the addition of the component of
each step.
Table 3 provides for the preparation of a 100 lb batch of AQ 323. The final
density of AQ
323 is 8.0696 lbs/ gallon.
Table 3. AQ323 Drift Reduction Agent
Step Component Weight Weight of Density of Volume of Component
Percent Component Component Added (gallons)
Added (lbs) lbs/gallon
Step AU810 40 40 7.5 5.33
1
Step TERWET 10 10 8.5 1.18
2
Step SOLEC 50 50 8.5 5.88
3 3F-UB
The volume of components to be added was determined by dividing the weight of
the
component to be added by the density of said component. AU810 is methylate
seed oil.
TERWET, as above, is tallow amine blended with emulsifier, comprising
approximately 78%
tallow amine and approximately 22% emulsifier. SOLEC 3F-UB is soy lecithin.
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[0086] AQ 284 combination water conditioning adjuvant and drift reduction
composition was prepared by combining 50% AQ 283 water conditioning adjuvant
and 50%
AQ 323 drift reduction agent. Table 4 provides for the preparation of a 100 lb
batch of AQ
284. The final density of AQ 284 is 8.6715 lbs/ gallon.
Table 4. AQ 284 Combination Water Conditioning Adjuvant and Drift Reduction
Agent
Step Component Weight Weight of Density of Volume of Component
Percent Component Component Added (gallons)
Added (lbs) lbs/gallon
Step AQ 283 50 50 9.37 5.34
1
Step AQ 323 50 50 8.07 6.20
2
Example 3: AQ 216 Water Conditioning Adjuvant
[0087] AQ 216 water conditioning adjuvant was prepared according to the
general
procedure as shown in Example 2 for AQ 283. AQ 216 contains 48% TERWET, 48%
sulfuric acid (98% concentrated) and 2% DEG.
Example 4: AQ 236 Combination Water Conditioning Adjuvant and Drift Reduction
Agent:
[0088] AQ 236 combination water conditioning adjuvant and drift reduction
agent
was prepared according to the general procedure as shown in Example 2. AQ 236
contains
38% TERWET; 4% sulfuric acid (98% concentrated); 32% DEG; 6.25% NP-9 (nonionic
surfactant); 6.25% MS0 and 12.5% lecithin.
Example 5: AQ 162 Combination Water Conditioning Adjuvant and Drift Reduction
Agent:
[0089] AQ 162 combination water conditioning adjuvant and drift reduction
agent
was prepared according to the general procedure as shown in Example 2. AQ 162
contains
30% TERWET; 4% sulfuric acid (98% concentrated); 25% DEG; 20% MSO and 21%
lecithin.
Example 6: AQ 163 Combination Water Conditioning Adjuvant and Drift Reduction
Agent:
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[0090] AQ 163 combination water conditioning adjuvant and drift reduction
agent
was prepared according to the general procedure as shown Example 2. AQ 163
contains 38%
TERWET; 4% sulfuric acid (98% concentrated); 32% DEG; 12.5% MS0 and 12.5%
lecithin.
Example 7: AQ 268 Drift Reduction Agent:
[0091] AQ 268 drift reduction agent was prepared by adding the components
of Table
in the order indicated. The components were added at room temperature and the
composition was mixed to homogeneity after the addition of the component of
each step.
Table 5 provides for the preparation of a 100 lb batch of AQ 268. The final
density of AQ
268 is 8.2988 lbs/ gallon.
Table 5. AQ 268 Drift Reduction Agent
Step Component Weight Weight of Density of Volume of Component
Percent Component Component Added (gallons)
Added (lbs) lbs/gallon
Step AU810 25 25 7.5 3.33
1
Step TERWET 15 15 8.5 1.76
2
Step DEG 10 10 9.35 1.07
3
Step SOLEC 50 50 8.5 5.88
4 3F-UB
[0092] The volume of components to be added was determined by dividing the
weight of the component to be added by the density of said component. AU810 is
methylate
seed oil. TERWET, as above, is tallow amine blended with emulsifier,
comprising
approximately 78% tallow amine and approximately 22% emulsifier. SOLEC 3F-UB
is soy
lecithin.
Example 8: Glyphosate Efficacy under Hard Water Conditions:
[0093] AQ 162 showed excellent hard water conditioning, reduced the pH of
the
spray solution which is beneficial for glyphosate efficacy and showed
excellent surfactant
effects as shown in the data of Figure 1 for the relative control of 4
indicator species by way
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of comparison to AIR LINK (commercial standard ¨ drift reduction agent) and
FULL LOAD
(water conditioning adjuvant).
Example 9: Percent of Droplets Less than 210, 150 and 105 microns:
[0094] AQ 162 and AQ 163 were compared with AMS, AIRLINK or INTERLOCK
in combination with ROUNDUP, in droplets size and percentage of smaller
droplets. AQ
162 showed equivalent reduction in terms of fine droplets (droplets less than
150 microns)
compared to commercial standards (AIRLINK and INTERLOCK) as shown in Figure 2.
Example 10: Evaluation of XR11002 Nozzle and Spray Solutions for Effects on
Droplet Size
Distribution
[0095] Spray solutions were analyzed with a Sympatec Helos Vario KF
particle size
analyzer. With a R6 lens installed, it is capable of detecting particle sizes
in a range from 0.5
to 1550 microns. This system uses laser diffraction to determine particle size
distribution.
The width of the nozzle plume was analyzed by moving the nozzle across the
laser by means
of a linear actuator. Five spray solutions were tested with a XR11002 nozzle
at 40 psi.
Results for droplet size are in Table 6.
[0096] The data of Table 6 show that AQ 284 provides equivalent increase
in droplet
size to the industry standard INTERLOCK at a 95% confidence level, reflected
in the percent
of droplets <150 microns belonging to statistical category "c" indicating that
33.14 and 32.87
are not statistically different at a 95% confidence level and the percent of
droplets <105
microns belonging to statistical category "d" indicating that 15.46 and 15.71
are not
statistically different at a 95% confidence level. While AQ 284 matches
"industry standard"
levels for increased droplet size, AQ 284 shows higher efficacy in field
efficiency percent
control of volunteer wheat.
[0097] In addition, the data of Table 6 show that AQ 284 reduced the
percent of
droplets under 150 microns in size, nearly 16% compared to RPM + AMS. AQ 284
provided
equivalent increase in droplet size as AQ 268 (drift reduction alone)
indicating that the
combination of water conditioning adjuvant in AQ 284 did not reduce efficacy
for increasing
droplet size.
Table 6. Spray Solution Additive Effects on Droplet Size and Consistency
Field Efficacy
Treatment Pct Pct Pct Relative % Control
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<105 !Am <150 imn > 730 [un Span Vol. Wheat
0
1. Water 16.14d 31.88c 0.00 a 1.30 cd
2. RPM + AMS 74
29.36 a 48.78 a 0.00 a 1.60 a
3. RPM + AMS + 92
INTERLOCK + NIS 15.46d 33.14 c 0.04a 1.26e
4. RPM + AQ 284 96
15.71 d 32.87 c 0.00 a 1.28 de
5. RPM + AQ 268 + AMS + 97
15.40 d 32.99 c 0.11 a 1.27 e
NIS
Spray tip = XR 11002 at 40 psi;
RPM = ROUNDUP POWER MAX at 22 oz/acre; AMS-Ammonium Sulfate at 17 lb/100 gal;
Nonionic Surfactant (NIS)=ACTIVATOR 90 at .25% v/v; AQ 284 or AQ 268 at .25%
v/v;
values within the same statistical category letter label (a-e) do not have any
statistical difference
from other values within the same statistical category letter label, at a 95%
confidence level
Example 11. Drift Reduction Testing of Combination Water Conditioning Adjuvant
and Drift
Reduction Composition
[0098] A study using a large electric fan was conducted out of doors with
the fan
wind blowing perpendicular to the direction of the spray pattern. A CO2
powered backpack
sprayer equipped with XR 11002 spray tips delivering 20 gpa at 40 psi was used
to make the
different spray treatments with dicamba. Petri dishes were placed downwind at
0, 2, 5, and 8
feet from the spray pattern. The petri dishes were collected, rinsed, and the
rinsate subjected
to HPLC analysis to quantify the amount of herbicide collected.
[0099] Table 7 provides study data for the amount of dicamba collected
from petri
dishes up to 8 feet away from the spray boom. The amount collected with no
drift reduction
was the least, indicating that the fine droplets in the spray without a drift
reduction agent
dried and floated out of the collection zone. The estimated drift loss from
the spray without a
drift reduction agent was 13%. The AQ 284 combination water conditioning
adjuvant and
drift reduction composition reduced the loss from drift to less than 5%. In
comparison to AQ
268 drift reduction agent alone, Table 7 shows that combining water
conditioning adjuvant
with drift reduction agent, as in AQ 284, resulted in minimal negative impact
on drift
reduction properties.
Table 7. Results of Drift Reduction Testing
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Capture
Distance Micrograms Theoretical
Treatment # Treatment Rate Feet Collected Captured %
1 AMS 17 lb /100 gal 0 391 77.26
Dicamba 0.5 lb /a 2 49 9.7
0 0
8 0 0
Total 440 86.96
2 AMS 17 lb /100 gal 0 383.86 75.77
Dicamba 0.5 lb /a 2 120.24 23.73
NIS 0.25 % v/v 5 2.71 0.53
INTERLOCK 4 oz/a 8 0.29 0.05
Total 507.1 100.08
3 ' AQ 284 0.25 % v/v 0 373.2 73.66
Dicamba 0.5 lb /a 2 104.95 20.72
5 3.95 0.77
8 2.63 0.51
Total 484.73 95.66
4 AQ 268 0.25% v/v 0 396.07 78.18
Dicamba 0.5 lb /a 2 84.28 16.34
5 6.83 1.35
8 1.28 0.25
Total 488.46 96.12
Example 12. Field Studies of Combination Water Conditioning Adjuvant and Drift
Reduction Composition
[00100] Two field studies were conducted to test the efficacy of the AQ 284
combination water conditioning adjuvant and drift reduction composition
compared to the
commercial standard (INTERLOCK). Studies consisted of 3 replications arranged
in a
randomized complete block design. The field studies were conducted in field
plots that were
x 30 feet in size which were wheat fallow fields under a linear irrigation
system where
supplemental irrigation was used to promote excellent weed growth. The weeds
in the test
area were common lambsquarter, kochia and redroot pigweed. The order of
increasing
susceptibility of these weeds was common lambsquarter, kochia and redroot
pigweed. The
study was conducted with hard water conditioned with a Zn acetate
micronutrient product,
AWAKEN, to provide a hard water cation level of 2,000 ppm. Field applications
were made
with a CO, powered backpack sprayer with a 6 nozzle boom.
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[00101] Table 8 shows the results of the field studies. AQ 284 at a rate of
0.5% v/v
had the best efficacy of drift reduction candidates. The AQ 284 formulation
demonstrated
equivalent or better efficacy as seen with the commercial standard which is a
combination of
three components consisting of: ammonium sulfate 17 lb/ 100 gallons of spray
solution +
0.25 % v/v nonionic surfactant + INTERLOCK 4 fluid ounces/acre.
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Table 8. Field Studies for Weed Control
Avg. Weed Avg. Weed
% Control % Control
TEST! TEST 2
46 Days After 31 Days After
Treatment # Treatment Name Rate Application Application
1 Untreated 0.0 0.0
2 TOUCHDOWN 0.70 lb/acre 11.7 78.3
HITEC
3 TOUCHDOWN 0.70 lb/acre 71.0 80.0
HITEC AMS 17 lb/100
gal
4 TOUCHDOWN 0.70 lb/acre 88.0 74.3
HITEC 17 lb/100
AMS gal
INTERLOCK 4 fl oz/acre
NIS 0.25% v/v
TOUCHDOWN 0.70 lb/acre 80.7 96.3
HITEC 0.25 % v/v
AQ 284
6 TOUCHDOWN 0.70 lb/acre 86.0 96.0
HITEC 0.50 % v/v
AQ 284
7 TOUCHDOWN 0.70 lb/acre 82.7 97.3
HITEC 0.25 % v/v
AQ 268
8 TOUCHDOWN 0.70 lb/acre 86.7 97.0
HITEC 2 qt/acre
FULL LOAD
Example 13. Greenhouse Study of Combination Water Conditioning Adjuvant and
Drift
Reduction Composition
[00102] A greenhouse
study was conducted to test the efficacy of the AQ 284
combination water conditioning adjuvant and drift reduction composition
compared to the
commercial standard (INTERLOCK). Greenhouse research was conducted with
individual
plants growing in 3 x 3 x 3 inch pots. Greenhouse treatments were applied with
a track
sprayer using an 8002 E single nozzle applying 20 gpa. When AQ 284 was added
to
glyphosate, it provided weed control, particularly at the 0.25 % v/v rate,
equivalent to the
commercial standard: glyphosate + INTERLOCK + ammonium sulfate + nonionic
surfactant.
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Table 9. Greenhouse Studies for Weed Control
Corn Sunflower
Wheat Average
% Control % Control % Control % Control
18 Days 18 Days 18 Days 18 Days
Trt Treatment After After After After
No. Name Rate Application Application Application Application
1 Untreated 0.0 0.0 0.0 0.0
2 Glyphosate 0.375 10.0 15.0 15.0 13.3
lb/acre
3 Glyphosate 0.375 65.0 70.0 50.0 61.7
AMS lb/acre
17 lb/100
gal
4 Glyphosate 0.375 60.0 75.0 40.0 58.3
AMS lb/acre
MIS 17 lb/100
INTERLOCK gal
0.25 % v/v
4 fl
oz/acre
Glyphosate 0.375 60.0 65.0 40.0 55.0
AQ 284 lb/acre
0.25 % v/v
6 Glyphosate 0.375 55.0 60.0 35.0 50.0
AQ 284 lb/acre
0.50% v/v
7 Glyphosate 0.375 50.0 65.0 45.0 53.3
AQ 268 lb/acre
0.25% v/v
Example 14. Drift Reduction Agents Comprising Emulsifier
[00103] Glyphosate Solutions were analyzed with a Sympatec Helos/Vario KR
particle
size analyzer. With the R7 lens installed, it is capable of detecting particle
sizes in a range
from 18 to 3500 microns. This system uses laser diffraction to determine
particle size
distribution. The width of the nozzle plume was analyzed by moving the nozzle
across the
laser by means of a linear actuator. All testing was performed in a low speed
wind tunnel at
mph. Spray solutions were evaluated through several nozzles, and each
treatment was
replicated at least three times. The nozzle tested was the XR11002 at 40 psi.
Results are in
the table that follows. The percent less than 105 tm (Pct <105 um) is the
percentage of the
spray volume that is 105 um and smaller, with percent less than 141[im (Pct
<141 um), 150
um (Pet <150 um), 210 um (Pet <210 um), and 730 um (Pct <730 um) being similar
measurements. The data were analyzed using a mixed model ANOVA (PROC MIXED)
with
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Replication set as random in SAS 9.2. The mean separation were conducted at
the a = 0.05
level using a Tukey adjustment.
Table 10. Droplet Size by Micron.
<105 <141 <150 <210 <730
Relative
LSD LSD LSD LSD LSD
Additive Span
a a 35.73 a 57.95 ab 100 a
1.42
18.48 32.25
NIS +AMS
AQ785 9.51
f 21.86 f 25.22 f 49.82 c 100 a 1.17
AQ790 10.06 f 23.15 f 26.67 f 51.97 de 100 a 1.18
AQ843 16.2
h 30.48 abc 34.13 abc 57.09 ah 100 a 1.35
AQ844 16.41 b 30.99 ah 34.71 ah 57.99 a 100 a 1.37
AQ796 14.5
d 28.59 cd 32.25 cd 56.18 abc 100 a 1.29
Interlock 12.13 e 25.51 e 29.05 e 52.91 de 100 a 1.24
[00104] In Table 10, NIS stands for non-ionic surfactant, AMS stands for
ammonium
sulfate, LSD stands for Least Significant Difference and Relative Span
indicates the variation
in droplet size. The greater the relative span number the more variation in
droplet size. The
codes in the LSD column indicate an LSD of 0.05. Treatments followed by the
same letter
are statistically similar and letters farther alphabetically apart indicate a
statistically greater
difference (e.g. a number where LSD is "a" is more different from a number the
LSD of
which is "f' than from a number the LSD of which is "b".
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[00105]
Table 11. Components of Additives
4% 8%
Additives Components of Additives H7SO4 AMADS AQ763
NIS+AMS
AQ785 Sulfonate Emulsifier 15 %+ Fatty Acid 40% + Not
MSO 30% + NIS Emulsifier 15% Not Stable Stable Stable
Sulfonate Emulsifier 6% + Fatty Acid 16% +
AQ790 MSO 30% + NIS Emulsifier 6% + Lecithin 36% Not
Amine Emulsifier 6% Not Stable Stable Stable
Not
AQ843 Sulfonate Emulsifier 25% + Fatty Acid 40% + Not Stable Stable
Stable
MSO 20% + NIS Emulsifier 15%
AQ844 Lecithin 40% + Fatty Acid 30% + MSO 15% + Not
NIS Emulsifier 15% Not Stable Stable Stable
AQ763 30% + TOMADOL 600 30% + AQ790
AQ796 40%
Not
INTERLOCK Not Stable Stable Stable
[00106] In Table 11. NIS stands for non-ionic surfactant; AMS stands for
ammonium
sulfate; the sulfonate emulsifier is calcium dodecylbenzene sulfonate; the
fatty acid consists
mostly of myristic, palmitic, stearic, oleic, linoleic and linolenic fatty
acids; MSO stands for
methylated seed oil; NIS emulsifier means emulsion forming non-ionic
surfactant; amine
emulsifier means emulsion forming amine surfactant; TOMADOL 600 is ethoxylated
linear
alcohol surfactant; AMADS is monocarbamide dihydrogen sulfate solution.
[00107] In the data of Table 10. the smaller the number in the column for
any
particular droplet size range (the fewer small droplets), the better the drift
reduction effect as
larger droplets travel less distance. Data is provided for INTERLOCK which is
the industrial
leader for drift control. Glyphosate alone (rows labeled NIS+AMS) serves as
the control in
the absence of drift reduction. A comparison of the data of Table 10 shows
that AQ 785 and
AQ 790 were more effective drift control agents than INTERLOCK.
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[00108] In the data of Table 11, it is apparent that the listed drift
reduction agents are
not stable in 4% H2SO4 and not stable in 8% AMADS, but are stable in AQ763.
[00109] Example 15. Water Conditioning Adjuvant Providing Water
Conditioning
(and in Some Embodiments Drift Reduction) While Not Increasing or Effectively
Decreasing
the Vaporization of Herbicides
[00110] Strong mineral acids added to polymers deliver a controlled amount
of acid
into a spray solution. The acid acts as a -hard water cation scavenger". In
one embodiment,
sulfuric acid is added to tallow amine. pH measurements of the combination of
polymer and
acid can be taken to show that free acid is present in the system. In one
embodiment, the pH
of the combination polymer and acid is higher that the pKa of the anionic
herbicide it is to be
used as an adjuvant for. Different mixtures were prepared as specified in
Tables 12-14.
Table 12
Load Out (Formula 21-1)
Water 65.9% wt
Tallow Amine 3780 30.0 % wt
SAG 10 0.1 % wt
(anti-foaming agent)
93% Sulfuric Acid 4.0 % wt
Table 13
Formula 21-2
Water 45.9% wt
Tallow Amine 3780 50.0 % wt
SAG 10 0.1 % wt
(anti-foaming agent)
93% Sulfuric Acid 4.0 % wt
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Table 14
Full Load
Diethylene Glycol 17.80 % wt
NP-10 50.0 wt
AU391 30 % wt
93% Sulfuric Acid 2.0 % wt
SAG 10 0.20 % wt
(anti-foaming agent)
[00111] The adjuvant produced by combining a polymer and an acid provides a
more
efficient method to condition water for agricultural spray application than
ammonium sulfate
(AMS). The adjuvant is prepared to maintain the pH above the pKa of anionic
herbicides.
The adjuvant works as well or better than AMS and efficiency is gained by
replacement of
large bags of dry AMS (17.5 lbs/ 100 gallons spray solution) or large volumes
(5 gallons/ 100
gallons of spray solution) of liquid AMS with 1 quart to 2 gallons of the
adjuvant per 100
gallons of spray solution. Also, the presently disclosed adjuvant, being a
liquid product, goes
into solution much faster than dry AMS goes into solution adding even more
efficiency. As
Figure 6 illustrates, the Load Out adjuvant of Table 12 causes much less
injury to plants from
vaporization of 2,4-D than AMS.
[00112] Cationic macromolecules make a stable mix with sulfuric acid.
Cationic
surfactant acts as a system that delivers enough free acid to tie up hard
water cations, while at
the same time the pH of the spray water is maintained at above the pKa of the
herbicide being
sprayed thus increasing the efficacy of the herbicide.
[00113] The adjuvants shown in Tables 12-14 increased or maintained the
efficacy of
anionic herbicides under hard water conditions much better than the addition
of AMS.
Further, it has been surprisingly found that the addition of an adjuvant
combining a polymer
and an acid, as in Table 12 or 14, does not increase or even reduces of
vaporization of
herbicides such as dicamba and 2,4-D, as shown in Figures 3-6. As Figures 3-4
and 6
illustrate, the Load Out adjuvant of Table 12 causes much less injury to
plants from
vaporization of dicamba or 2,4-D than other leading adjuvants. As Figures 3
and 5 illustrate,
the Full Load adjuvant of Table 14 causes much less injury to plants from
vaporization of
dicamba or 2,4-D than other leading adjuvants. Adjuvants as disclosed herein
which
combine a polymer and acid with drift reduction, also providing the benefit of
not increased
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or reduced vaporization of herbicides such as dicamba and 2,4-D. For example,
the Full
Load Complete drift reducing adjuvant as described in Example 12 has been
shown in
Figures 3 and 5 to provide the benefit of reduced volatility of dicamba or 2,4-
D.
[00114] The results of standard volatility box test for dicamba DGA salt
are illustrated
at Figures 3-4 comparing the adjuvants described in Table 12 (Load Out), Table
14 (Full
Load) and Example 12 (Full Load Complete) with competitor adjuvants HEL-FIRE
and
BRIMSTONE. Clarity which is the industry standard dicamba DGA salt provides
the
negative control as well as being combined with the tested adjuvants. The
vaporization tests
were performed with soybeans 10 to 20 cm tall with at least 1 fully expanded
trifoliate.
Three indicator plants were placed inside inverted, opaque plastic boxes, 57
cm x 38 cm x 30
cm in size. Two glass petri dishes. 9 cm in diameter, containing 10 mls of
each treatment
mix were placed open inside the volatility boxes on a greenhouse bench and
left for 48 hours
after which the plants were placed (outside of the box) on the greenhouse
bench.
[00115] The results of the standard volatility box tests for 2,4-D DMA salt
are
illustrated at Figures 5-6 comparing the adjuvant described in Table 12 (Load
Out), Table 14
(Full Load) and Example 12 (Full Load Complete) with competitor adjuvants HEL-
FIRE and
BRIMSTONE. 2,4-D DMA is the dimethyl amine salt of 2,4-D. 2,4-D DMA provides
the
negative control as well as being combined with the tested adjuvants. The
vaporization tests
were performed with tomato plants. 14-24 cm tall with 3 to 6 fully expanded
leaflets. Three
indicator plants were placed inside inverted, opaque plastic boxes, 57 cm x 38
cm x 30 cm in
size. Two glass petri dishes, 9 cm in diameter, containing 10 mls of each
treatment mix were
placed open inside the volatility boxes on a greenhouse bench and left for 48
hours after
which the plants were placed (outside of the box) on the greenhouse bench.
[00116] The foregoing embodiments and examples are intended only as
examples. No
particular embodiment, example, or element of a particular embodiment or
example is to be
construed as a critical, required, or essential element or feature of any of
the claims. Further,
no element described herein is required for the practice of the appended
claims unless
expressly described as "essential" or "critical." Various alterations,
modifications,
substitutions, and other variations can be made to the disclosed embodiments
without
departing from the scope of the present invention, which is defined by the
appended claims.
The specification, including the figures and examples, is to be regarded in an
illustrative
manner, rather than a restrictive one, and all such modifications and
substitutions are
intended to be included within the scope of the invention. Accordingly, the
scope of the
invention should be determined by the appended claims and their legal
equivalents, rather
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than by the examples given above. For example, steps recited in any of the
method or
process claims may be executed in any feasible order and are not limited to an
order
presented in any of the embodiments, the examples, or the claims.
43
